US20120029255A1 - Process for converting a heavy feed into gasoline and propylene, having an adjustable yield structure - Google Patents

Process for converting a heavy feed into gasoline and propylene, having an adjustable yield structure Download PDF

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US20120029255A1
US20120029255A1 US13/060,457 US200913060457A US2012029255A1 US 20120029255 A1 US20120029255 A1 US 20120029255A1 US 200913060457 A US200913060457 A US 200913060457A US 2012029255 A1 US2012029255 A1 US 2012029255A1
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gasoline
propylene
catalytic cracking
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Romina Digne
Olivier Callebert
Romain Roux
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
    • C10G63/04—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only including at least one cracking step
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • the invention relates to a process for conversion of a heavy hydrocarbon feed, having high flexibility regarding the production of gasoline and propylene. More precisely, the process of the present invention can co-produce gasoline in a minimum yield and propylene with a yield which may reach 10% of the weight of the feed.
  • the minimum yield of gasoline depends on the starting feed, but routine feeds such as vacuum distillates or atmospheric residues, this minimum yield is more than 40%, and preferably more than 45% by weight with respect to the entering feed.
  • the FCC process can convert heavy hydrocarbon feeds the initial boiling point of which is generally more than 340° C. to lighter hydrocarbon fractions, in particular a gasoline cut, by cracking molecules of the heavy feed in the presence of an acid catalyst.
  • FCC also produces liquefied petroleum gas (LPG) in large quantities with high olefins contents.
  • LPG liquefied petroleum gas
  • the propylene yield is obtained to the detriment of the gasoline yield and is associated with relatively severe operating conditions.
  • the gasoline yield is maintained at a minimum value which clearly depends on the nature of the feed and the catalyst used, even when the operating conditions are determined with a view to maximizing the propylene production.
  • the process of the present invention can thus generally be presented as a process for the co-production of propylene and gasoline with a minimum gasoline yield.
  • the process employs, in succession, the reactions of catalytic cracking and oligomerization of olefins from the C3/C4 cut, or from the C4 cut, or from the C4/C5 cut, the term Cn denoting a cut of hydrocarbons containing n carbon atoms.
  • This process produces gasoline with a minimum yield which is generally more than 40% by weight with respect to the entering feed and propylene in a yield which can be adjusted within a wide range, which for certain feeds can be up to 10% by weight.
  • the present invention is compatible with all catalytic cracking reactor technologies, whether using riser or dropper technology.
  • Patent FR-2 837 213 describes a process for conversion of a heavy feed which comprises a step for catalytic cracking, selective hydrogenation and oligomerization of olefins containing 4 and/or 5 carbon atoms derived from catalytic cracking.
  • the heavy feed and the oligomers are cracked together or separately with the same catalyst.
  • the cracking effluents are separated in a common fractionation zone.
  • a portion of the C4 or C4/C5 cut obtained after fractionation is oligomerized. When the C4 cut is oligomerized then cracked as a secondary feed, this process increases the propylene yield while retaining the gasoline yield.
  • the process of the present invention can increase the propylene yield while slightly increasing the gasoline yield, but it offers in addition the possibility of substantially increasing the gasoline yield and the capacity of the unit if the propylene production is no longer desired, all using the same facility and without changing the catalyst.
  • Patent FR-2 837 100 describes a process for producing propylene and gasoline comprising at least one step for oligomerization and a step for catalytic cracking of the oligomers formed.
  • the oligomers formed from olefins containing 4 and/or 5 carbon atoms are cracked in a catalytic cracking unit to form large quantities of propylene.
  • the feed for the process of the cited patent is thus a “light” hydrocarbon feed with a boiling point of less than 340° C.
  • the process of the present invention concerns the conversion of a heavy feed with a boiling point of more than 340° C. in order to obtain a lot of gasoline and more or less propylene.
  • FIG. 1 shows a flow chart for the process of the invention in its “maxi propylene” regime
  • FIG. 2 shows a flow chart for the process of the invention in its “maxi gasoline” regime.
  • the invention concerns a process for conversion of a hydrocarbon feed termed a heavy feed, i.e. constituted by hydrocarbons with a boiling point of more than approximately 340° C., with a view to the co-production of propylene and gasoline with a minimum yield.
  • a hydrocarbon feed termed a heavy feed, i.e. constituted by hydrocarbons with a boiling point of more than approximately 340° C.
  • the process of the invention comprises at least two reaction steps, a first catalytic cracking step and a second step for oligomerization of C3 and C4 olefins, or C4 olefins or C4 and C5 olefins, derived from catalytic cracking.
  • a third reaction step for selective olefin hydrogenation may in certain cases be necessary before oligomerization.
  • the process of the invention means that two types of production corresponding to two distinct regimes can be carried out:
  • One of the advantages of the invention is to be able to swing over time from one to the other of the two regimes defined above. It is also possible to operate the unit in any intermediate mode between the “maxi propylene” and “maxi gasoline” regimes.
  • This swing is very simple to carry out as it essentially consists of modifying the feed entering the oligomerization unit without substantially modifying the operating conditions of the catalytic cracking unit and the oligomerization unit and clearly without modifying the catalysts used.
  • the process for co-production of gasoline and propylene from a hydrocarbon feed with an initial boiling point of more than 340° C. of the invention uses a catalytic cracking unit followed by an oligomerization unit which can function in accordance with two regimes termed “maxi propylene” (regime 1 ) and “maxi gasoline” (regime 2 ) in which:
  • the catalytic cracking unit may be broken down into several modalities with a single reactor processing the heavy feed and the light feed or two reactors, one processing the heavy feed and the other processing the light feed. Further, each reactor may function in riser or dropper mode.
  • the overall feed to be cracked contains more than 50% by weight of hydrocarbons with a boiling point of more than 340° C.
  • the feed is constituted by a vacuum distillate or possibly an atmospheric residue.
  • the overall cracked feed may contain up to 100% by weight of hydrocarbons with a boiling point of more than 340° C. for the “maxi gasoline” mode.
  • the feed usually contains more than 60% by weight, and more usually more than 70%, for example between 70% and 95% by weight of hydrocarbons with a boiling point of more than 340° C.
  • the secondary feed for catalytic cracking required in the “maxi propylene” mode generally contains 2% to 40% by weight, more usually 4% to 30% by weight and more preferably 6% to 25% by weight, of a cut which is rich in olefins essentially constituted by olefins containing 8 carbon atoms which have been produced by oligomerizing olefins containing 4 (or 4 and 5) carbon atoms.
  • This oligomer cut may also contain non-negligible quantities of paraffins.
  • the secondary feed may also comprise other oligomers essentially formed from C2 to C10 olefins.
  • the cracking catalyst is the same for the “maxi propylene” and for the “maxi gasoline” mode. It is a catalyst constituted by an ultra stable Y type zeolite dispersed in an alumina, silica or silica-alumina matrix to which an additive based on ZSM-5 zeolite is added, the total quantity of ZSM-5 crystals in the cracking unit being less than 10% by weight.
  • the invention can be defined as a process for the co-production of gasoline and propylene from a hydrocarbon feed with an initial boiling point of more than or equal to 340° C., said process using a catalytic cracking unit followed by an oligomerization unit which can function in accordance with two regimes termed “maxi propylene” (regime 1 ) and “maxi gasoline” (regime 2 ) in which:
  • the catalytic cracking unit may comprise a single reactor processing both the heavy feed and the light feed or two distinct reactors, one processing the heavy feed, the other processing the light feed. Further, each of the reactors may be in riser or dropper mode. Usually, the two reactors will have the same mode of flow.
  • the reactor outlet temperature (ROT) is in the range 510° C. to 580° C., preferably in the range 540° C. to 590° C., and the C/O ratio is in the range 8 to 20; 2) When the reactor is in dropper mode, the reactor outlet temperature (ROT) is in the range 550° C. to 590° C. and the C/O ratio is in the range 15 to 50; 3) When the catalytic cracking is carried out in two distinct FCC reactors in dropper mode, the first FCC reactor carrying out cracking of the heavy feed operates at a reactor outlet temperature (ROT 1 ) in the range 510° C.
  • the second FCC reactor carrying out cracking of C8+ reactors from the oligomerization unit operates at a reactor outlet temperature (ROT 2 ) in the range 550° C. to 650° C., preferably in the range 570° C. to 620° C., with a C/O ratio in the range 8 to 25.
  • the first FCC reactor carrying out cracking of the heavy feed operates at a reactor outlet temperature (ROT 1 ) in the range 550° C. to 700° C.
  • the second FCC reactor operating cracking of the C8+ oligomers from the oligomerization unit operates at a reactor outlet temperature (ROT 2 ) in the range 570° C. to 700° C., with a C/O ratio in the range 15 to 50.
  • ROT 2 reactor outlet temperature
  • the reactor outlet temperature (ROT) of each cracking reactor is in the range 500° C. to 580° C., preferably in the range 520° C. to 550° C., and the C/O ratio is in the range 5 to 10.
  • the reactor outlet temperature (ROT) of each cracking reactor is in the range 530° C. to 650° C., and the C/O ratio is in the range 15 to 25.
  • the streams of used catalyst derived from the two FCC reactors are separated from the cracking effluents using any gas-solid separation system which is known to the skilled person and regenerated in a common reference zone.
  • the effluent from the catalytic cracking reactor (or the two effluents if there are two FCC reactors) is sent to a fractionation zone to produce a plurality of cuts including a gasoline cut and a cut containing olefins:
  • This cut containing 3 and 4 (denoted C3/C4) or 4 (denoted C4) or 4 and 5 (denoted C4/C5) carbon atoms is sent for oligomerization. It is generally preferable for this cut to undergo selective hydrogenation to reduce the diolefinic compounds and/or acetylenic compounds which may be present in order to increase the oligomerization cycle time.
  • the separation unit constituted by one or more distillation columns is adjusted to allow extraction of the C4 or C4/C5 cut or the C3/C4 cut.
  • the major portion or all of the oligomers produced is added to the gasoline cut obtained by fractionation of the catalytic cracking effluent.
  • the gasoline yield, with respect to the quantity of hydrocarbons with a boiling point of more than 340° C. is thus generally in the range 35% to 65% by weight, usually in the range 50% to 60% by weight.
  • the propylene yield with respect to the quantity of hydrocarbons with a boiling point of more than 340° C. is then generally less than 1% by weight and this propylene is in general not specifically recovered.
  • “maxi propylene” mode a portion, i.e. at least 30%, and preferably all of the oligomers produced, is recycled to catalytic cracking.
  • the gasoline yield, with respect to the quantity of hydrocarbons with a boiling point of more than 340° C. is then generally in the range 35% to 55% by weight, usually in the range 40% to 50% by weight.
  • the propylene yield with respect to the quantity of hydrocarbons with a boiling point of more than 340° C. is then generally in the range 4% to 20% by weight, usually in the range 5% to 15% and more usually in the range 7% to 12% by weight.
  • the catalyst for the FCC reactor is typically used in the foil of a fine powder with a mean particle diameter which is generally in the range 40 to 140 micrometres, usually in the range 50 to 120 micrometres.
  • the catalyst for catalytic cracking contains at least one Y type zeolite dispersed in an appropriate matrix such as alumina, silica or silica-alumina.
  • the catalyst may also comprise at least one zeolite with form selectivity with one of the following structure types: MEL (for example ZSM-11), MFI (for example ZSM-5), NES, EUO, FER, CHA (for example SAPO-34), MFS, MWW, or it may also be one of the following zeolites: NU-85, NU-86, NU-88 and IM-5, which also has form selectivity.
  • MEL for example ZSM-11
  • MFI for example ZSM-5
  • NES EUO
  • FER FER
  • CHA for example SAPO-34
  • MFS MWW
  • the advantage of these zeolites with form selectivity is that better propylene/isobutene selectivity is obtained, i.e. with a propylene/isobutene ratio which is higher in the cracking effluents.
  • the proportion of zeolite with form selectivity with respect to the total quantity of zeolite may vary as a function of the feeds used and of the desired product structure. Frequently, 2% to 60% is used, preferably 3% to 40% and in particular 3% to 30% by weight of zeolite(s) with form selectivity.
  • the zeolite or zeolites may be dispersed in a silica, alumina or silica-alumina based matrix, the proportion of zeolite (all zeolites together) with respect to the weight of catalyst usually being in the range 3% to 80% by weight, preferably in the range 4% to 50% by weight, for example in the range 5% to 25% by weight.
  • the proportion of zeolite (all zeolites together) with respect to the weight of catalyst usually being in the range 3% to 80% by weight, preferably in the range 4% to 50% by weight, for example in the range 5% to 25% by weight.
  • they may be incorporated into a single matrix or into a plurality of different matrices.
  • the total amount of zeolite with form selectivity is less than 10% by weight.
  • the catalyst used in the catalytic cracking reactor may be constituted by an ultra stable Y type zeolite dispersed in an alumina, silica or silica-alumina matrix to which an additive based on ZSM-5 zeolite is added, the total quantity of ZSM-5 crystals being less than 10% by weight.
  • the unit for separating the catalytic cracking reactor effluents generally comprises a primary separation of the FCC effluents, a section for compression and fractionation of gases as well as distillations for fractionation of the various liquid cuts.
  • fractionation unit is well known to the skilled person and depends on the intended end result.
  • the C4 cut or the C4/C5 cut is separated from the effluents to send it for oligomerization, and if necessary for selective hydrogenation before oligomerization.
  • the C3/C4 cut is separated from the effluents to send it for oligomerization, and if necessary for selective hydrogenation before oligomerization.
  • the olefinic cuts from catalytic cracking which are sent for oligomerization may be mixed with olefin-rich cuts imported from other units such as C3/C4 cuts or C4 cuts deriving from a cokefaction unit, steam cracking unit, methanol-olefin conversion unit, etc.
  • isobutene may be extracted, for example by etherification of isobutene by an alcohol, then by distillation, to prevent or limit the presence of isobutene in the oligomerization step, this compound tending to form isomers which can re-crack to isobutene in the FCC, which tends to result in accumulation of this compound if a sufficient isobutene purge is not carried out.
  • extractive distillation for example with a solvent which may be N-methyl pyrrolidone (NMP) or dimethylsulphoxide (DMSO) or an isomer thereof, to extract the unsaturated fraction from the paraffins in the feed which are then mixed with the solvent.
  • NMP N-methyl pyrrolidone
  • DMSO dimethylsulphoxide
  • the C4 or C4/C5 cut or the C3/C4 cut of the FCC effluents contains a small quantity of dienes (diolefins) and acetylenes which increase coking of the oligomerization catalyst and thus reduce the cycle time of the oligomerization reactor. Selective hydrogenation of dienes and acetylenes to mono-olefins is thus preferable in the process of the invention, although it is not vital.
  • the principal aim of this step is to transform the diolefins (or dienes) into mono-olefins.
  • the mono-olefins are the source of the oligomers produced in oligomerization step 3.
  • Another aim of this step is to eliminate traces of acetylenic hydrocarbons present in these cuts since they are unwanted compounds as regards oligomerization.
  • the acetylenic compounds are also transformed into mono-olefins.
  • the residual quantity of diolefins+acetylenics of the selective hydrogenation effluent is typically less than approximately 1000 ppm by weight, preferably less than 100 ppm by weight, and more preferably less than 20 ppm by weight.
  • this selective hydrogenation step is carried out using a catalyst comprising at least one metal selected from the group formed by nickel, palladium and platinum, deposited on a support comprising alumina, silica or silica-alumina.
  • the quantity of palladium on the support may typically be 0.01% to 5% by weight, preferably 0.05% to 1% by weight.
  • the operating temperature for the selective hydrogenation is generally in the range 0° C. to 200° C.
  • the pressure typically is in the range 0.1 to 5 MPa, usually in the range 0.5 to 5 MPa
  • the hourly space velocity is typically in the range 0.5 to 20 m 3 per hour per m 3 of catalyst, preferably in the range 0.5 to 5 m 3 per hour per m 3 of catalyst
  • the H 2 /(acetylenic+diolefinic compounds) molar ratio is generally in the range 0.5 to 5, preferably in the range 1 to 3.
  • one or more fixed bed reactors is used, in downflow co-current mode for the feed to be processed and the hydrogen (or a gas containing a substantial molar fraction of hydrogen, for example at least 50%), or in downflow mode for the feed to be processed and upflow mode for the hydrogen (or hydrogen-rich gas).
  • the aim of this step is to oligomerize C4 or C4/C5 olefins (“maxi propylene” regime) or C3/C4 olefins (“maxi gasoline” regime) to obtain a mixture of hydrocarbons containing mono-olefins with a number of carbon atoms equal to eight or more.
  • oligomers are obtained which mainly contain 30 or fewer carbon atoms, primarily in the range 8 to 20 carbon atoms.
  • Oligomerization is distinguished from polymerization by adding a limited number of molecules, the number of added molecules in the context of the invention being in the range 2 to 10, limits included, and generally in the range 2 to 5, in particular in the range 2 to 4.
  • the oligomers may, however, include traces of olefins which have been oligomerized with a number of molecules exceeding 10. Usually, these traces represent less than 5% by weight with respect to the oligomers fowled.
  • Oligomerization may be carried out in one or more steps, with one or more reactors and one or more catalysts.
  • the following description of the catalyst and the operating conditions may be applied to any one of the steps and/or any one of the reactors:
  • FIGS. 1 and 2 The invention will now be explained in more detail with the aid of the description of FIGS. 1 and 2 .
  • FIG. 1 shows the facility for carrying out the process of the invention in the “maxi propylene” operating regime.
  • the vacuum distillate or atmospheric residue feed is introduced via line 1 .
  • the catalytic cracking reactor (R 1 ) is supplied via two separate lines 1 and 9 .
  • the effluents from the catalytic cracking (R 1 ) are evacuated via line 2 and introduced into a separation zone S 1 .
  • the separation zone S 1 typically comprises a gas compressor and distillation/absorption means.
  • the C3+C4 cut of the effluents from the catalytic cracking reactor (R 1 ) is sent to the separation zone S 2 via line 4 .
  • the gasoline corresponding to a C5-220° C. cut is evacuated via line 15
  • the other FCC effluents are evacuated via line 3 .
  • the separation zone S 2 typically comprises distillation means.
  • the C3 cut containing mainly propylene is evacuated via line 5 .
  • the highly olefinic C4 cut is sent to the oligomerization reactor R 2 via line 6 .
  • the oligomerization effluents are extracted via line 7 and introduced into a separation zone S 3 .
  • the separation zone S 3 typically comprises distillation of the oligomerization effluents to recover the heavier oligomers, and the unreacted C4 cut.
  • the C4 cut is mainly constituted by paraffinic compounds and a minority of untransformed olefinic compounds. This C4 cut is evacuated via line 8 .
  • the C8+ oligomers are partially and preferably completely introduced into the catalytic cracking reactor R 1 via line 9 , the line 14 corresponding to oligomers which are not recycled to R 1 .
  • the major portion of the remaining oligomers are mixed with the gasoline from catalytic cracking.
  • Cracking the oligomers in R 1 means that the propylene yield of the facility can be increased.
  • FIG. 2 shows the facility for carrying out the process of the invention in “maxi gasoline” regime.
  • the catalytic cracking reactor R 1 is supplied with vacuum distillate or atmospheric residue via line 1 .
  • the C3+C4 cut from the FCC effluents is sent to the oligomerization reactor R 2 via line 10 .
  • the C3+C4 cut which has not reacted in R 2 is sent to the separation zone S 2 via line 12 .
  • the C4 cut, separated from the C3 cut in S 2 is evacuated via line 13 .
  • the C6+ oligomers formed are not recycled and form a gasoline cut (line 11 ) which joins up with the gasoline cut from the catalytic cracking reactor (line 15 ).
  • the gasoline produced by the process is thus constituted by a combination of effluents from lines 15 and 11 .
  • the pressure in the reaction zone was equal to 0.2 MPa and the operating conditions for the “maxi propylene” and “maxi gasoline” regimes were as follows:
  • FIG. 1 Illustrated in FIG. 1
  • the C4 cut of the catalytic cracking effluent was separated in the separation zone S 1 then S 2 , then introduced into the oligomerization reactor R 2 which operated under the following conditions:
  • the oligomerization catalyst was amorphous silica-alumina.
  • FIG. 1 Propylene 9.3 C4 cut 5.9 Gasoline (C5-220° C.) 49.0
  • FIG. 2 Illustrated in FIG. 2
  • the C3+C4 cut separated in the separation zone S 1 was introduced into the oligomerization reactor R 2 which operated under the following conditions:
  • the oligomerization catalyst was amorphous silica-alumina.
  • FIG. 2 Propylene 0.2 C4 cut 4.2 Gasoline (C5-220° C.) 55.2
  • the gasoline yield was increased by 8 points (55.2 ⁇ 47.1) compared with the prior art “maxi gasoline” regime.
US13/060,457 2008-08-29 2009-07-29 Process for converting a heavy feed into gasoline and propylene, having an adjustable yield structure Abandoned US20120029255A1 (en)

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FR08/04759 2008-08-29
FR0804759A FR2935377B1 (fr) 2008-08-29 2008-08-29 Procede de conversion d'une charge lourde en essence et en propylene presentant une structure de rendement modulable
PCT/FR2009/000945 WO2010023369A1 (fr) 2008-08-29 2009-07-29 Procédé de conversion d'une charge lourde en essence et en propylène présentant une structure de rendement modulable

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US20140135557A1 (en) * 2012-11-12 2014-05-15 Uop Llc Process for fluid catalytic cracking oligomerate
WO2014074984A1 (en) * 2012-11-12 2014-05-15 Uop Llc Process for oligomerizing gasoline without further upgrading
US9278893B2 (en) 2012-11-12 2016-03-08 Uop Llc Process for making gasoline by oligomerization
EP2917170A4 (en) * 2012-11-12 2016-06-29 Uop Llc PROCESS FOR OLIGOMERIC FLUID CATALYTIC CRACKING
US9434891B2 (en) 2012-11-12 2016-09-06 Uop Llc Apparatus for recovering oligomerate
US9441173B2 (en) 2012-11-12 2016-09-13 Uop Llc Process for making diesel by oligomerization
US9522375B2 (en) 2012-11-12 2016-12-20 Uop Llc Apparatus for fluid catalytic cracking oligomerate
US9522373B2 (en) 2012-11-12 2016-12-20 Uop Llc Apparatus for oligomerizing light olefins
US9567267B2 (en) 2012-11-12 2017-02-14 Uop Llc Process for oligomerizing light olefins including pentenes
US9644159B2 (en) 2012-11-12 2017-05-09 Uop Llc Composition of oligomerate
US9663415B2 (en) 2012-11-12 2017-05-30 Uop Llc Process for making diesel by oligomerization of gasoline
US9670425B2 (en) 2013-12-17 2017-06-06 Uop Llc Process for oligomerizing and cracking to make propylene and aromatics
US9732285B2 (en) 2013-12-17 2017-08-15 Uop Llc Process for oligomerization of gasoline to make diesel
US9914673B2 (en) 2012-11-12 2018-03-13 Uop Llc Process for oligomerizing light olefins

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FR2968010B1 (fr) * 2010-11-25 2014-03-14 Ifp Energies Now Procede de conversion d'une charge lourde en distillat moyen
FR2984916B1 (fr) * 2011-12-23 2014-01-17 IFP Energies Nouvelles Procede ameliore de conversion d'une charge lourde en distillat moyen faisant appel a un pretraitement en amont de l'unite de craquage catalytique
FR2986799B1 (fr) * 2012-02-15 2015-02-06 IFP Energies Nouvelles Procede de conversion d'une charge lourde, mettant en oeuvre une unite de craquage catalytique et une etape d'hydrogenation selective de l'essence issue du craquage catalytique
CN109369319B (zh) * 2018-12-07 2021-11-12 宁波旭合瑞石化工程有限公司 一种以c4-c8烯烃为原料最大化生产丙烯的方法
CN111718753B (zh) * 2019-03-22 2021-10-08 中国石油化工股份有限公司 一种多产丙烯的催化转化方法和系统
CN111718754B (zh) * 2019-03-22 2021-11-16 中国石油化工股份有限公司 一种生产汽油和丙烯的方法和系统
CN111825514B (zh) * 2020-08-12 2021-06-01 浙江科茂环境科技有限公司 一种乙烯或丙烯最大化的生产方法

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9567267B2 (en) 2012-11-12 2017-02-14 Uop Llc Process for oligomerizing light olefins including pentenes
US9522375B2 (en) 2012-11-12 2016-12-20 Uop Llc Apparatus for fluid catalytic cracking oligomerate
US9278893B2 (en) 2012-11-12 2016-03-08 Uop Llc Process for making gasoline by oligomerization
EP2917170A4 (en) * 2012-11-12 2016-06-29 Uop Llc PROCESS FOR OLIGOMERIC FLUID CATALYTIC CRACKING
US20140135557A1 (en) * 2012-11-12 2014-05-15 Uop Llc Process for fluid catalytic cracking oligomerate
US9441173B2 (en) 2012-11-12 2016-09-13 Uop Llc Process for making diesel by oligomerization
WO2014074984A1 (en) * 2012-11-12 2014-05-15 Uop Llc Process for oligomerizing gasoline without further upgrading
US9522373B2 (en) 2012-11-12 2016-12-20 Uop Llc Apparatus for oligomerizing light olefins
US9434891B2 (en) 2012-11-12 2016-09-06 Uop Llc Apparatus for recovering oligomerate
US9644159B2 (en) 2012-11-12 2017-05-09 Uop Llc Composition of oligomerate
US9663415B2 (en) 2012-11-12 2017-05-30 Uop Llc Process for making diesel by oligomerization of gasoline
US10508064B2 (en) 2012-11-12 2019-12-17 Uop Llc Process for oligomerizing gasoline without further upgrading
US9914673B2 (en) 2012-11-12 2018-03-13 Uop Llc Process for oligomerizing light olefins
US9834492B2 (en) * 2012-11-12 2017-12-05 Uop Llc Process for fluid catalytic cracking oligomerate
US9732285B2 (en) 2013-12-17 2017-08-15 Uop Llc Process for oligomerization of gasoline to make diesel
US9670425B2 (en) 2013-12-17 2017-06-06 Uop Llc Process for oligomerizing and cracking to make propylene and aromatics

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WO2010023369A1 (fr) 2010-03-04
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MX2011001923A (es) 2011-03-30
KR101605927B1 (ko) 2016-03-23
CN102137914B (zh) 2014-02-26
JP2012500883A (ja) 2012-01-12
BRPI0917844A2 (pt) 2015-11-24
RU2011111688A (ru) 2012-10-10
FR2935377A1 (fr) 2010-03-05
KR20110048560A (ko) 2011-05-11
JP5520952B2 (ja) 2014-06-11
MX344256B (es) 2016-12-09
FR2935377B1 (fr) 2013-02-15
BRPI0917844B1 (pt) 2018-02-06
EP2321385A1 (fr) 2011-05-18
CN102137914A (zh) 2011-07-27

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